A family of tri- and dimetallic pyridine dicarboxamide cryptates: unusual O,N,O-coordination and facile access to secondary coordination sphere hydrogen bonding interactions.

A series of tri- and dimetallic metal complexes of pyridine dicarboxamide cryptates are reported in which changes to the base and metal source result in diverse structure types. Addition of strong bases, such as KH or KN(SiMe3)2, followed by divalent metal halides allows direct access to trinuclear complexes in which each metal center is coordinated by a dianionic N,N,N-chelate of each arm. These complexes bind a guest K(+) cation within the central cavity in a trigonal planar coordination environment. Minor changes to the solvent and equivalents of base used in the syntheses of the triiron(II) and tricobalt(II) complexes affords two trinuclear clusters with atypical O,N,O-coordination by each pyridine dicarboxamide arm; the amide carbonyl O atoms are oriented toward the interior of the cavity to coordinate to each metal center. Finally, varying the base enables the selective synthesis of dinuclear nickel(II) and copper(II) complexes in which one pyridine dicarboxamide arm remains protonated. These amide protons are at one end of a hydrogen bonding network that extends throughout the internal cavity and terminates at a metal bound hydroxide, carbonate, or bicarbonate donor. In the dinickel complex, the bicarbonate cannot be liberated as CO2 either thermally or upon sparging with N2, which differs from previously reported monometallic complexes. The carbonate or bicarbonate ligands likely arise from sequestration of atmospheric CO2 based on the observed reaction of the di(hydroxonickel) analog.

Preorganized assembly of three iron(II) or manganese(II) ß-diketiminate complexes using a cyclophane ligand.

A trinucleating cyclophane bearing three ß-diketimine arms, and the corresponding iron(II) and manganese(II) complexes have been synthesized and characterized. The three metal ions are oriented towards the internal void space, and are coordinated by a N2Br2 donor set, in which a unique combination of µ(3), µ, and terminal coordination modes are observed for the halide donors.